CHEMICAL ENGINEERING DESIGN

CE 420
Energy balances

1
Conservation of energy
 Energy is conserved separately from mass in all processes except
nuclear reactions.
 Energy conservation differs from mass conservation as follows:
1. Total mass into a unit must equal total mass flow out at steady
state.
 Holds even when new chemical species are formed due to
reactions.
2. Total energy of the inlets, however, will not be equal to that of
outlets at steady state if energy is consumed or generated.
 I.e. due to heat of reaction.
2
Conservation of energy
 Energy exits in several forms i.e., internal, heat, mechanical etc.

 Total energy i.e. sum of all different forms of energy involved is what
is conserved.

 In process design, energy balances are used for:

1. Determining the heating, cooling and power requirements of a unit

or process.

2. Energy audit to show pattern of energy usage and to suggest ways

to conserve energy.

3
Conservation of energy
 The general equation for the conservation of energy is

Energy output = Energy input + generation – consumption - Accumulation

 For steady-state, accumulation = 0.

 Above is a mere statement of the first law of thermodynamics.
 Balance equation can be applied to any process step or unit.
 Generation and consumption terms are mainly energy evolved
(exothermic) or absorbed (endothermic) during a reaction.
 Energy balances can be more complex than material balances.
4
Forms of energy – per unit mass
1. Potential energy – energy due to elevation above a reference.
𝑃𝐸 = 𝑔𝑧 (4.1)
 Where 𝑔 and 𝑧 are the local gravitational acceleration and elevation
from reference.
2. Kinetic energy – energy due to motion where 𝑢 is the velocity (m/s)
1 2
𝐾𝐸 = 𝑢 (4.2)
2

3. Internal energy – energy associated with molecular motion and

structure.
𝑈 = 𝑓(𝑡) (4.3)
5
Forms of energy – per unit mass
4. Work – energy expended when force moves through distance.
𝑙
𝑊= ‫׬‬0 𝐹𝑑𝑥 (4.4)

 Convention: work done by system is +ve and that done on system is –

ve.
 If work is as a result of change in pressure and volume, then
2
𝑊= ‫׬‬1 𝑃𝑑𝜐 (4.5)

 Where 𝑃 is the pressure (N m-2), 𝜐 is specific volume (m3/kg).

 Can be integrated when relationship between 𝑃 and 𝜐 is known.
6
Forms of energy – per unit mass
 Eq. 4.5 is normally used to estimate the work required in expanding
or compressing a gas.
 Work is estimated depending on nature of process, e.g.,
1) No heat exchange between system and surroundings is involved,
 Reversible adiabatic is assumed, for which 𝑃 and 𝜐 are related by:
𝑃𝜐 𝛾 = 𝑐𝑜𝑛𝑠𝑡 (4.6)
 Where 𝛾 = 𝐶𝑃 Τ𝐶𝜐 .
2) Reversible isothermal for which 𝑃 and 𝜐 are related by:
𝑃𝜐 = 𝑐𝑜𝑛𝑠𝑡 (4.7)
7
Forms of energy
 Heat energy – energy transferred between system and its
surroundings due to difference of temperature between them.

 System does not contain heat or work.

 Though transfer of these changes internal energy.

 Electrical and mechanical energy – included in the energy balance

through the work term.

8
Energy balance
Inlet
 Consider a steady-state process shown
Q
(1)

in the figure below:

 Conservation of energy can be written

Z1

W Outlet

to include various forms of energy. (2)

Z1

 On a unit mass basis:

Fig. 4.1 Conservation of energy
1 2 1 2
𝑢1 + 𝑝1 𝜐1 + 𝑣 + 𝑔𝑧1 + 𝑄 = 𝑢2 + 𝑝2 𝜐2 + 𝑣 + 𝑔𝑧2 + 𝑊 (4.8)
2 1 2 2

 𝑄 represents heat transferred across system boundary, +ve if added

to system, otherwise –Ve.

9
Energy balance
 𝑊 is the work done on or by system, +ve for work from system to
surroundings, otherwise –Ve.

 KE and PE usually small compared to heat or work in chemical

processes.

 Can be neglected and 𝑢 + 𝑝𝜐 can be taken as enthalpy, ℎ i.e.,

ℎ = 𝑢 + 𝑝𝜐 (4.9)

 It is a function of both temperature and pressure, more of a function

of temperature only for solids and liquids.

 Values can be obtained from literature for common substances.

10
Energy balance
 Can also be calculated from specific and latent heat data if not known.

 Above energy conservation equation reduces to:

ℎ1 + 𝑄 = ℎ2 + 𝑊 𝑜𝑟 ℎ2 − ℎ2 = 𝑄 − 𝑊 (4.10)

 Sufficient for estimating the heating and cooling requirement for

process units.

 Applies to both flow and non-flow systems.

 If the work is zero as is the case for many units, then

𝑄 = ℎ2 − ℎ2 (4.11)
11
Energy balance
 In processes where heat is generated i.e. due to heat of reaction then

𝑄 = 𝑄𝑝 + 𝑄𝑔 (4.12)

 Where 𝑄𝑔 is the heat generated, +ve for exothermic process where

heat is evolved and –ve for endothermic where heat is absorbed.

 𝑄𝑝 is the process heat added to system i.e., to maintain temperature.

 Eq. 4.11 then becomes

𝑄𝑝 + ℎ2 − ℎ2 −𝑄𝑔 (4.13)

 ℎ1 and ℎ2 are enthalpies of inlet and outlet streams.

12
Example 4.1
Estimate the steam and cooling requirement for QC

the distillation column in the figure operating at 1 Distillate, D

bar.
Feed, F

Dry saturated steam is available at 25 psi (274 kPa

abs) and cooling water temperature rise is limited QB
to 30℃. Bottoms, W

Heat capacity and stream data:

Component Cp (kJ/kg K) Feed (w/w) Distillate Bottoms
𝐶3 𝐻6 𝑂 (Acetone) 25 – 35℃ 2.2 10% 99% >100 ppm
𝐻2 𝑂 (water) 25 – 100℃ 4.2 90% 1%
Flow rate (kg/h) 1000
Temperature (℃) 35 25 100
13
Specific enthalpy from Cp
 Values are available in literature for some more common materials.
 If not reported anywhere, specific enthalpy can be calculated as
𝑇
ℎ 𝑇 = ‫𝑇𝑑 𝑝𝐶 𝑇׬‬ (4.14)
𝑟

 Where:
 ℎ 𝑇 = specific enthalpy at temperature T.

 𝐶𝑝 = specific heat capacity of the material at constant pressure.

 𝑇𝑟 = is the reference temperature.

14
Specific enthalpy from Cp
 For process involving phase transition, latent heat for phase change is
added to sensible heat determined as
𝑇𝑝 𝑇
ℎ𝑇 = ‫𝑝𝐶 𝑇׬‬1 𝑑𝑇 + ‫𝑝𝐶 𝑇׬‬2 𝑑𝑇 (4.15)
𝑟 𝑝

 Where:
 𝑇𝑝 = phase transition temperature.

 𝐶𝑝1 = specific heat capacity of first phase below 𝑇𝑝 .

 𝐶𝑝2 = specific heat capacity of second phase above 𝑇𝑝 .

 𝑇𝑟 = is the reference temperature.

15
Specific enthalpy from Cp
 𝐶𝑝 varies with temperature so that using Eq. 4.14 and 4.15 requires
expression for 𝐶𝑝 as a function of temperature.
 𝐶𝑝 as function of temperature is normally expressed as empirical high-
order polynomial:
𝐶𝑝 = 𝑎 + 𝑏𝑇 + 𝐶𝑇 2 + 𝑑𝑇 3 or 𝐶𝑝 = 𝑎 + 𝑏𝑇 + 𝐶𝑇 −1/2 (4.16)

 For first expression, temperature may be specified as K or ℃.

 Whereas the second expression requires absolute temperature (K).

16
Example 4.2
Estimate the specific enthalpy of ethyl alcohol at 1 bar and 200ŽC, taking
the reference temperature as 0℃ .

Data:
At 0℃, 𝐶𝑝 = 24.65 cal/mol℃ and at 100℃ 𝐶𝑝 = 37.96.65 cal/mol℃.

For ideal gas state:

𝐶𝑝𝑜 𝑇 = 14.66 + 3.758 × 10−2 𝑇 − 2.091 × 10−5 𝑇 2 + 4.740 × 10−9 𝑇 3

Boiling point at 1 bar = 78.4℃.
Latent heat of vaporisation = 9.22 kcal/mol.
17
Mean heat capacities
 Makes it much more convenient to calculate sensible heat changes
and enthalpies of process streams.
 Since a single constant value 𝐶𝑝 can be used for a temperature
range.
 For a temperature range 𝑇1 to 𝑇2 , mean specific heat capacity can
be defined as:
𝑇2 𝑇2
𝐶𝑝,𝑚 = ‫𝑇𝑑 𝑝𝐶 𝑇׬‬ ÷ ‫𝑇𝑑 𝑇׬‬ (4.17)
1 1

 Mean specific heat capacities for some common substances are

tabulated in literature.

18
Mean heat capacities
 If mean specific heats data are available, then specific enthalpy
change between 𝑇1 and 𝑇2 is
∆ℎ = 𝐶𝑝,𝑚 𝑇2 𝑇2 − 𝑇𝑟 − 𝐶𝑝,𝑚 𝑇2 𝑇1 − 𝑇𝑟 (4.18)
 Where 𝐶𝑝,𝑚 𝑇2 was calculated from 𝑇2 and 𝑇𝑟 and 𝐶𝑝,𝑚 𝑇1 from
𝑇1 and 𝑇𝑟 .
 When 𝐶𝑝 is expressed as a third-order polynomial in 𝑇, Eq. 4.17
becomes
𝑏 2 𝑐 3 𝑑 4
𝑎 𝑇 − 𝑇𝑟 + 2 𝑇 − 𝑇𝑟 + 3 𝑇 − 𝑇𝑟 + 4 𝑇 − 𝑇𝑟
𝐶𝑝,𝑚 = (4.19)
𝑇 − 𝑇𝑟

19
Mean heat capacities
 T is the temperature at which 𝐶𝑝,𝑚 is to be evaluated.

 For 𝑇𝑟 = 0 then 4.20 becomes

𝑏 𝑐 2 𝑑 3
𝐶𝑝,𝑚 =𝑎 + 𝑇 + 𝑇 + 𝑇 4.20
2 3 4
 Also, the specific enthalpy change from 𝑇1 and 𝑇2 can be expressed
as

∆ℎ = 𝐶𝑝,𝑚 𝑇2 𝑇2 − 𝐶𝑝,𝑚 𝑇2 𝑇1 (4.21)

20
Example 4.3
The gas leaving a combustion chamber has the following composition:
CO2 7.8, CO 0.6, O2 3.4, H2O 15.6, N2 72.6, all volume percentages.
Calculate the heat removed if the gas is cooled from 800 to 200℃.

The mean specific heat capacities for the combustion gases is as

follows:

Mean Cp (kJ/kmol ℃)
Component 𝑁2 𝑂2 𝐶𝑂2 𝐶𝑂 𝐻2 𝑂
200℃ 29.29 29.95 40.15 29.51 34.12
800℃ 30.77 32.51 47.94 31.10 37.38

21
Cp – effect of pressure
 Specific heat data reported in handbooks is usually for the ideal gas
state.
 Also called ideal gas state specific heat i.e., obtained by assuming
ideal gas behaviour and normally written
𝐶𝑝𝑜 𝑇 = 𝑎 + 𝑏𝑇 − 𝑐𝑇 2 + 𝑑𝑇 3 (4.22)
 Corresponds to low pressures where gas or vapor can be assumed
to be ideal.
 Effect of pressure is neglected for as long as pressures are not too
high.
 Specific heat can then be used for real gases at low pressures.

22
Cp – Effect of pressure
 For high pressures, a pressure correction
to the ideal gas state Cp is required.

 Excess heat capacity chart such as

reproduced here can be used.

 Plots isothermal pressure correction to

ideal state Cp as a function of reduced
pressure and temperature.

 Fig. 4.2 was prepared for hydrocarbons

but can apply to other vapours or gases.
Fig. 4.2 Excess heat capacity chart
23
Example 4.4
The ideal state specific heat capacity of ethylene is given by the
expression:
𝐶𝑝𝑜 𝑇 = 3.95 + 15.6 × 10−2 𝑇 − 8.3 × 10−5 𝑇 2 + 17.6 × 10−9 𝑇 3
Estimate the value of the specific heat at 10 bar and 300 K.
Critical properties for ethylene are:
Critical pressure = 50.5 bar
Critical temperature = 283 K

24
Enthalpy of mixtures
 In most heat balances, heat of mixing can be neglected for:

 (i) Gases and (ii) organic compounds that are similar in structure
(usually from same family).

 No significant errors will be introduced in the design calculations.

 Heat capacity and enthalpy can be taken as weighted-average.

𝐶𝑝 𝑚 = 𝑥𝐴 𝐶𝑝𝐴 + 𝑥𝐵 𝐶𝑝𝐵 + 𝑥𝐶 𝐶𝑝𝐶 + ⋯ (4.23)

 Where 𝑥𝐴 , 𝑥𝐴 , 𝑥𝐶 etc. are mol fractions of components A, B and C.

25
Enthalpy of mixtures
 For liquid mixtures and solutions, heat of mixing or solution can be
significant.

 This must be part of the calculated mixture enthalpy.

 For a mixture of two components, enthalpy can be expressed as

ℎ𝑚 𝑇 = 𝑥𝐴 ℎ𝐴 + 𝑥𝐵 ℎ𝐵 + ∆ℎ𝑚 𝑇 (4.24)

 Where ℎ𝐴 and ℎ𝐵 are the specific enthalpies for A and B.

 ∆ℎ𝑚 𝑇 is the heat of mixing or solution at temperature T.

26
Enthalpy of mixtures
 Heats of mixing or solution are determined experimentally.

 Such values are reported in literature for common substances.

 If not available judgment must be made whether or not to include

heat of mixing, e.g.,

1) Organic solutions, heat of mixing can be neglected in a heat balance.

2) Organic and inorganic compounds in water typically have significant

heats of solution.

 Especially mineral acids and strong alkalies.

27
Integral heats of solution
 Heat of solution: Enthalpy change when 1 mole of a solute (gas or
solid) completely dissolves in a specified amount of solvent at
constant temperature.

 Depends on final concentration.

 Integral heat of solution - cumulative heat released or absorbed in

preparing a solution of a given concentration.

 Standard integral heat of solution: Limiting value of integral heat of

solution at infinite dilution.

 Heats of solution data is available over a range of concentrations as:

28
Integral heats of solution
 Tables or plots for some common substances.

 Data can be used to determine heating or cooling requirements in

preparing process solutions.

Example 4.5
A solution of NaOH in water is prepared by diluting a concentrated
solution in an agitated vessel. The strength of the concentrated solution
is 50 per cent w/w and 2500 kg of 5 per cent w/w solution is required
per batch. Calculate the heat removed by the cooling water if the
solution is to be discharged at a temperature of 25℃. The temperature
of the solutions fed to the vessel can be taken to be 25℃.
29
Example 4.5
Mol H2O per −∆𝑯𝒐𝒔 (kJ/mol 45
Wt%
mol NaOH NaOH) 40

35

-ΔHs(kJ/mol NaOH)
1 69.0 11.3
30
2 52.6 21.1 25

3 42.5 28.9 20

4 35.7 34.4 15

10
5 30.7 37.8 0 2 4 6 8 10 12

Mol H2O/mol NaOH

6 27.0 39.9
8 21.7 41.9 Fig. 4.3 heat of solution vs concentration
10 18.0 42.5
15 12.9 42.8
20 10.0 42.9

30
Example 4.5
 Temperature of the feeds may not always be equal to that of the
final product.

 In this cases, reference temperature is taken for the energy

balance.

 Usually the temperature at which standard integral heat of solution

was determined i.e. 25℃.

 Enthalpies of the feeds are then determined relative to the

reference temperature.

 And are included in the energy balance.

31
Enthalpy concentration diagrams
 Used to simply the calculation of
energy balances on liquid-phase
systems.

 H-x diagram shows the variation of

specific enthalpy of a binary mixture
with concentration.

 Normally the enthalpy on such

figures covers phase change from
solid – liquid – vapour.
Fig. 4.4 Enthalpy-concentration chart
for NH3-H2O system
32
Enthalpy concentration diagrams
 Fig. 4.4 shows a typical enthalpy-concentration diagram for NH3-H2O.

 Enthalpy variation with concentration is depicted with pressure and

temperature as parameters.

 Of importance on such figures are the reference state.

 I.e. states at which enthalpies of pure components are taken as zero.

 For Fig. 4.4, reference states are -77℃ for NH3 and 0℃ for H2O.

 E.g. for 20 wt% NH3-H2O solution at 40℃, ∆ℎ𝑚 = 130 kJ/kg mixture.

33
Enthalpy concentration diagrams
 For adiabatic mixing of two solutions, two feed conditions and the
final condition lie on the same straight line.

 I.e. (𝑥1 , ℎ1 or 𝑇1 ), (𝑥2 , ℎ2 or 𝑇2 ) and final solution (𝑥3 , ℎ3 or 𝑇3 ).

 If mass and composition of initial solutions is known, final mixture

composition is
𝑥1 𝑚2 + 𝑥2 𝑚1
𝑥= (4.25)
𝑚1 + 𝑚2

 Thus, line connecting two feed conditions can be drawn on 𝐻 − 𝑥

diagram.

34
Enthalpy concentration diagrams
 Intersection of this line and vertical line
for final composition gives the enthalpy
of the mixture under adiabatic
conditions.

 Isotherm cutting through intersection

gives the final temperature.

 As an example: maximum temperature Fig. 4.5 Mixture enthalpy

when liquid ammonia at 40℃ is dissolved under adiabatic conditions
in water at 20 ℃ to form a 20 wt%
solution is 40℃.

35
Heats of reaction
 For a process with a chemical reaction, heat is either removed or
added.

 Since reactions are characterised by heats of reaction.

 The quantity depends on conditions at which reaction is carried out.

 Standard heat of reaction ∆𝐻𝑟𝑜 - heat released or absorbed per mole

of either reactant of product under standard conditions
(25℃, 𝐼 𝑎𝑡𝑚).

 Heats of reactions are available in literature or can be calculated

from standard heats of formation.
36
Heats of reaction
 Basis when stating heat of reaction must be explicitly stated.
 Can be either mole of reactant or product or the reaction is
indicated.
 For process design, ∆𝐻𝑟𝑜 is normally specified per mole of product
for conditions under which reaction is carried out.
 State of reactants and products should also be specified.
 For exothermic, ∆𝐻𝑟𝑜 is –ve and +ve for endothermic reaction.
 ∆𝐻𝑟𝑜 can be converted to heat of reaction at any temperatures
using:
37
Heats of reaction
∆𝐻𝑟 𝑇 = ∆𝐻𝑟𝑜 + ∆𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡 − ∆𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 (4.26)

 Where ∆𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 is enthalpy

change to bring reactants to
standard temperature.
 ∆𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡 is enthalpy change to
bring reaction products to reaction
temperature T.
Fig. 4.6 Converting ∆𝐻𝑟𝑜 to that
at any reaction temperature

38
Heats of reaction
 Reactants and products may be at different temperatures from
that of the reaction.
 Energy balance can be carried out using standard temperature for
heat ∆𝐻𝑟𝑜 as the reference.
 Then it is not necessary to correct the standard heat of reaction.
 Heat balance for reactor can be written as
𝑄𝑝 = 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡 − 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 − 𝑄𝑟 (4.26)
 Where 𝑄𝑝 is heat added or removed to maintain reactor
temperature.

39
Heats of reaction
 𝑄𝑟 is the total heat generated evaluated from standard heat of
reaction.

𝑄𝑟 = ෍ −∆𝐻𝑟𝑜 × 𝑚𝑜𝑙𝑠 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 (4.27)

Example 4.6
Vinyl chloride (VC) is manufactured by the pyrolysis of
1,2,dichloroethane (DCE). The reaction is endothermic. The flow-rates
to produce 5000 kg/h at 55 per cent conversion are shown in the
diagram. The reactor is a pipe reactor heated with fuel gas, gross
calorific value 33.5 MJ/m3. Estimate the quantity of fuel gas required.

40